DE2409951A1 - ION EXCHANGE MATERIAL - Google Patents

Description

1974

Sven Erik J ^ rgensea, DK-35OO Vaerlöse, Langkaer Vaenge 9, Denmark

Ion exchange material

The invention relates to an ion exchanger: material for Removal of dissolved high molecular organic compounds, ÄHEttonium ions and phosphate ions from water and a waste water treatment method using the ion exchange material.

Bach a belcanned process is to be processed Wastewater from a mechanical or biological pretreatment, for example, to remove solid, high molecular weight Subject to substances. The wastewater pretreated in this way is then passed over an ion exchange bed to remove the dissolved organic compounds, salts, toxic compounds or Schvennetalle.

For this purpose, anion exchangers were based on used by polystyrene, clinoptinolite or cellulose.

The polystyrene exchangers are suitable for removing phosphate ions and in some cases also for removing more toxic ones Compounds as well as heavy metals present in anion form, for example for the removal of chromate

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ions. However, the pliosphate ions are found to be satisfactory I'asr. removed, näralidi "u at least about 90 Vo.

'... it i'Ilino ^ tinolit can v / ground ÄL'cimoniuvaionen away, but without this having a noticeable effect on the other contaminations.

i'it HiI: -; e of cellulose exchangers can be proteins removed, but practically no other connections or ions.

VTeiterhin is a method for Bsseitijun-j of At / snoniak from 'described in the .iasser! J3-I-.J 674,430, according to which is ^v ater geleibet? A basic Iuistauscherraaterial. This exchanger material was initially loaded with long anions, which were then oxidized to form manganese oxides. '

"Further, in US-PS 3,222,277 a process for the removal of dissolved: described 3isen of iron-containing water, the water running over activated carbon particles after the one, which are impregnated with in eitu produced Liangan (IV) oxide.

The invention is based on the object of an ion exchange material to create the Auuaoniak at the same time, Phosphate ions and dissolved high molecular weight organic compounds, especially proteins, with high efficiency can remove from sewage; the exchange material should be able to be eluted and regenerated in one step. Farther The invention is based on the object of creating a wastewater treatment method with which in a single Level antononia, phosphate ions and dissolved high molecular weight

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Substances, especially proteins, are removed from the soil.

To achieve this object "ard erfindungsgeiriäss aiii exchanger material proposed, which is characterized in that the I-iUßtauschervaaterial a nit γ-! Manganese (IV) -o :: id impregnated cellulose-lo-isnauGtaus-cli r- ^ material.

For the implementation of the treatment process erfindungsgenäss värd suggested that :: aan the AEbv; ater with j'ällunjsmitteln and Όγλτ. or Äus.31oc] cuagsr _i itteln treated and that the so pretreated water is then allowed to run through a cellulose exchanger bed impregnated with y-manganese (IV) oxide.

It is completely surprising that the AusGliermaterial the invention not only Äinmonia3c and solved Proteins, but also 1-phosphate ions from de ^ ii removed. The exchange material of the invention up to et ^^ 150 phosphorus per liter of exchanger material from a solution containing phosphate ions. At the same time, Ainraoniuraxons ground in a close of up to 2500 rag iHI ^ per liter aufgenorrien.

A significant advantage of the exchange material of the The invention also resides in the fact that the carrier material from cheap raw materials, namely from cellulose products can be produced.

The preparation of ion exchange material of the invention is carried out preferential prices in such a way that, to a mixture of a Celluloseaustauscliermaterials and a base, for example HaOIi, Iialiu ± apermanganat and the mixture thus obtained to a temperature in the range of 00 - heated 95 ⁰ C. That so

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Get the fast product is separated and r-i.with water

"a-ii a bevorsujtsn i * us guide horn of jSrfin ^; lestaat das 2sllulof5eaustaus: £ iemafcerial from bark e:! er : ii "do or sulphonated bark or bark.

■ door Preparation of sulfonieirten Borkennaterials v ^r ird the bark, for example .Tichtenborke, cut into small pieces and Roit 50 - SO; cent SChv / efelsäure 30-120 min Ιε.η-2 'treated. Even untreated spruce wood has a protein absorption capacity of 0.3 killie equivalent per liter. The previously described treatment of the bark with sulfuric acid increases this absorption capacity to about 0.6 ililli equivalent per liter.

The exchange material of the invention is suitable especially for wastewater treatment. Wastewater, the high molecular weight organic compounds, ammonium ions and phosphate ions contained in dissolved:? orin can be practically completely discharged / earthed.

The wastewater is used to carry out the water treatment initially with precipitants and Lsvr. or flocculants ! Deals. The water treated in this way is then used via the target exchange material of the invention directed.

! times a preferred embodiment of this method vd-rd the outlet from the cellulose exchanger then passed through an activated carbon bed impregnated with γ-manganese (IV) oxide. Through the described in the The treatment carried out in the sequence becomes a qualitatively and quantitatively particularly effective wastewater treatment achieved. By finally passing through the activated carbon bed impregnated with γ-manganese (IV) oxide

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__ ^ J ——

becomes an even more effective removal of the phosphabions and the ararnonium ions. At the same time, dissolved low molecular weight compounds are removed.

Another advantage of the replacement material of the invention lies in the fact that it can be eluted with sodium hydroxide solution. If the jSluatio, is-. processes can include all fliospliations and Äm> .io: iiui. \ - nitrogen ions are eluted.

Those converted to ammonia at the pH of the bluing agent Ammonium compounds can be extracted from the eluate in easily removed by going into the sluat blows air. The egg is expediently heated, for example to 35 - 40 C.

The organic substances can be removed from the eluate together with the phosphates by suspending calcium hydroxide. As a result, 80 % of the organic compounds and 90 % of the phosphates are precipitated. If the eluate treated in this way is left to stand for a few hours, a clear phase over a sludge phase is obtained in a length of 75-80% of the total volume.

In practice it has been shown that y-Kangan (IV) oxide is gradually washed out along with the water. The amounts of manganese dioxide discharged in this way however, they are very small. The product water has manganese concentrations that are in any case below 0.1 mg / l lie. With regard to the quality of the product water, this manganese concentration is completely insignificant and negligible. The exchange capacity of the exchange material however, it gradually decreases as the kangan dioxide is washed out. After ten eggs of the exchange material is its exchange

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.1

capacity only 95 Vo of the initial value. Uach additional 15 Eluationen, ie after a total of 25 Hluationen, the exchange capacity is about au2 / 83 - sunk> of the original TJertes. Uta counteract this decrease in the exchange capacity, the raw water may be in front of the object to the IIanv_; of (lV) -o; cid-3etcea I'aliumpemanganat be added. Y ^ L in such lucats takes place twice in about every twentieth regeneration. The potassium permanganate is preferably added in quantities of about 50 xag potassium permanganate per liter of Ilohvasser. Additions in this amount are sufficient to obtain the full capacity of the manganese dioxide contained in the ion exchange material. On average, this rate corresponds to an addition of 2.5 mg potassium peranganate per liter of wastewater.

The invention is nimbly based on exemplary embodiments described in more detail »

3 example 1

300 l of sulfonated lignocellulose (chloride number: 21) were mixed with 175 lm of NaOH solution. The mixture is heated to 80 ° C. Over the course of 2 hours, a total of 45 kg of Kl-InO- are added in powder form. After addition of all potassium permanganate, the mixture 1 is "allowed to stand ti at 80-95 C. During the addition of the potassium permanganate and the subsequent reaction is directed to the stirring of the mixture air. The total reaction time is 3 _f 5 h. The solid product is then separated and washed with water to remove the liquor and fine particulate matter.

100 ral parts of the material thus obtained are used to Used treatment of solutions that contain various amounts of ammonium ions and phosphate ions. The effect

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degree and the exchange capacity of the exchange material. The results obtained are in
the following table I -susanx-aen ^ e

Table I.

Starting N-NH ₄ ⁺ 100 30 10 10 10 1

Koiisentration _

(mg / 1) ^p - ^po / i Ir ^{0 1} T 0 1, -0 10 30 '10

concentration

(mg / 1) after

Passes of _N + ₆ ^. ^ _{5 Qf6} ^ _{5 Ofl}

¹ II. 3_

, ... " ^P " ^PO 4 ° r ⁰⁵ ° r ⁰⁴ ° f ⁰⁵ ° ' ^{5 1} T ^{0 1} T ⁰ '

N-NH. " ¹ " 10 3 1.0 1.1 1.0 0 _f l

■ 5 1st V.

P-PO ₄ 0.05 Ar ° 6 0.1 1.2 3.0 4.8

. ': ■'' N-NH ₄ ⁺ 23.5 2.0 1.2 2.1 0.2

1Ö 1>% _

P-PO ₄ ^J 0.07 0.06 0.2 3 _t 5 8.0 9.6

_; .- .; £. N-NH ₄ ⁺ 47 8 3.2 2.9 3.0 0.2

P-PO ₄ ³ "0.10 0.12 0.5 8.9 12.5 6.9

N-NH ₄ ⁺ 82 '26 5 4, G. 6.5 0.2

20 1% ■

P-PO ₄ ^J 0 _T 18 0 _f 2 0.9 9.5 27.0 10 _f 3

(mg / 1) N-NH ₄ ⁺ 7300 270Q * Ϊ200 1200 1200 200

P-PO " ³ " 200 190 100 600 1300 200

The capacity of the ion exchange material is as
Total recording of the exchange material at one point in time

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defines the efficiency is decreased to 80%.

The data shown in Table I show that the removal of HH _{4 is} practically independent of the PO ~ concentration. However, the toy distance increases with increasing IIH. ^ Concentration. Without tying the finding or this effect to a theory, which is essential to the invention, the view is expressed that obviously TH ^ is partly adsorptively, partly chemisorptively taken up by the exchanger. The chemisorption takes place by surface precipitation as MnNKLPO ₄ . The phosphate ions, on the other hand, can only be absorbed by the exchanger material by chemisorption, but not by adsorption.

The exchange material produced in the manner described above was also used for the treatment of municipal waste water. The wastewater was treated with a precipitant and then placed in a settling tank.

The wastewater pretreated in this way then became the following treatment steps subject.

1) cellulose sexon exchanger;

2) cellulose _{sexon exchanger coated with 1'InO 2 and}

3) cellulose _{sexon exchanger coated with 1InO 2} and then activated carbon coated with MnO _2.

In all three treatment cases, the volume ratio of raw water to exchanger is 100: 1. The results obtained with the aforementioned three types of treatment are compiled in Table II below.

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Table II

Pre-treated RoIl-VTa s s he

Treatment Treatment 3handlur (1) (2), (3)

KT-InO. -Number
(rag 8 ₀ / l)

56

50

10

BOD _ς number

92

52

50

Protein concentrations
tration (mg / 1) 6th 0.8 0.8 0.6 M total (mg / 1) 32 25th 8 _r 6 ² T ¹ IT-IH ₄ ⁺ (mg / 1) 26th 24 6.9 l _f 6 P-PO ₄ ³ "(rag / l) 0 _f 82 0.79 0.12 0.06 COD number (mg 0 ₂ / l) 250 156 • 156 30th P total (mg / 1) 0.96 ' 0.92, 0 _f 15 0.04

From the data compiled in Table II it can be seen that the total nitrogen content and the total phosphorus content are determined by the rait MnO _? coated cellulose exchangers could be reduced considerably. The effect achieved in this way can be further increased by giving the outlet of the BlnO ^ cellulose exchanger over an MnO ₂ activated carbon bed.

The order in which the water to be treated is given over the two treatment beds is included important because the cellulose exchanger is much less sensitive

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against constipation by hoclr.iolel: ulare organic Connections than the Alctivlcohlebett is.

Example 2

Fish search water was through. I-Iiridurchleitea through a bed of sulfonated lignocellulose, which was coated with Y-lJiO ,, and then passing through a bed of ::: dt L * nO _? coated active carbon cleaned. The water was passed through each bed with a flow rate of 5 ri ^ / h. After 3 h the Gesar.Tc'TasDernen-je treated ainraal in each of the beds.

The received. The results are shown in Table III below put together.

Table St.

(rag 3_ / U (ng O./1) (mg / D (ag / I)

before the

75 O ₁ S

treatment 30th after treatment -.

0.05 0.2

The data in Table III clearly shows that both the total phosphorus content and the ammonium ion nitrogen as a result of the treatment described ^T .-. ^T eG-3 is slightly reduced \\ Ordsn. At the same time, the content of high molecular weight organic compounds is also substantially prevented.

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Claims (5)

Claims [I) ion exchange material κιϊγλ removal of dissolved high molecular weight organic Ver'oinduivjen,.: \: I? I? IMoniuraionen and phosphate ions from water, characterized in that the 2-exchange material is a cellulose ion exchange material impregnated with y-IIanjan (IV) oxide . 2. "Ion exchange material according to claim 1, characterized in that that the cellulose from exchangeable material .bark material is. 3. Ion exchange material according to claim _1, characterized in that the cellulose exchange material is sulphonated boron material. 4. waste water treatment process for removing dissolved high molecular weight organic compounds, ammonium ions and phosphate ions, characterized in that the waste water is labeled with I ^; Treated precipitants and / or flocculants and that the waste water pretreated in this way is then allowed to run through a cellulose exchanger bed impregnated with γ-Ilangan (IV) -o: od. 5. The method according to claim 4, characterized in that the water is then passed to the cellulose exchanger through an activated carbon bed impregnated with γ-manganese (IV) oxide runs. 409836/0911